1. Field of the Invention
This invention relates to a process of making a mixed metal oxide catalyst containing oxides of molybdenum, bismuth, iron, cesium, antimony and other metals for the production of unsaturated aldehydes from olefins, such as methacrolein by gas phase catalytic oxidation of isobutylene in the presence of air or another gas containing molecular oxygen.
2. Description of the Prior Art
Typically, the catalyst for oxidation of isobutylene to methacrolein is a mixed metal oxide prepared by mixing compounds containing the desired elements in a solution or a suspension and drying the resulting concentrate. Thereafter, the dried product is calcined. The calcined product may be ground or formed to a mesh size suitable for use. The prepared catalyst can be prepared with a specific surface area. The catalysts may be supported on a suitable carrier, such as silica, silica-containing materials, silicon carbide, alumina and the like, in order to improve the physical properties of the catalysts. Many methods of making catalysts for use in the production of acrolein or methacrolein by catalytic vapor phase oxidation of propylene or isobutylene have been disclosed.
U.S. Pat. No. 4,816,603 discloses a catalyst for production of methacrolein and methacrylic acid of the formula:MoaWbBicFedNieSbfXgYhZiAjOkwhere X is potassium, rubidium and/or cesium, Y is phosphorus, sulfur, silicon, selenium, germanium and/or boron, Z is zinc and/or lead, A is magnesium, cobalt, manganese and/or tin, a is 12, b is 0.001 to 2, c is 0.01 to 3, d is 0.01 to 8, e is 0.01 to 10, f is 0.01 to 5, g is 0.01 to 2, h is 0 to 5, i is 0.01 to 5, j is 0 to 10 and k is sufficient to satisfy the valences. The method of preparation disclosed was that solution A of ammonium molybdate, ammonium paratungstate and rubidium nitrate and solution B of bismuth nitrate, ferric nitrate, nickel nitrate, magnesium nitrate and zinc nitrate were formed, solution B was added to solution A to form a slurry and antimony trioxide was added to the slurry.
U.S. Pat. No. 4,511,671 discloses a catalyst for manufacturing methacrolein of the formula:MoaWbBicFedAeBfCgDhOxwhere A is at least one of nickel and/or cobalt; B is at least one of alkali metals, alkaline earth metals and/or thallium; C is at least one of phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese and/or zinc; D is at least one of silicon, aluminum, zirconium, and/or titanium; a is 12, b is 0 to 10, c is 0.1 to 10, d is 0.1 to 20, e is 2 to 20, f is 0 to 10, g is 0 to 4, h is 0 to 30 and x is determined by the atomic valences. The method of preparation disclosed was that cobalt nitrate and ferric nitrate were dissolved in water and separately bismuth nitrate was dissolved in water and nitric acid. These two solutions were mixed and then added to another solution of ammonium paramolybdate and ammonium paratungstate dissolved in water. A solution of cesium nitrate dissolved in water and a solution of silica sol were also added.
U.S. Pat. No. 4,556,731 discloses a catalyst for production of methacrolein and methacrylic acid of the formula:AaBbFecXdMeMO12Oxwhere A is an alkali metal, such as potassium, rubidium, cesium or mixtures thereof, thallium, silver or mixtures thereof, B is cobalt, nickel, zinc, cadmium, beryllium, calcium, strontium, barium, radium or mixtures thereof, X is bismuth, tellurium or mixtures thereof and M is (1) Cr+W, Ge+W, Mn+Sb, Cr+P, Ge+P, Cu+W, Cu+Sn, Mn+Cr, Pr+W, Ce+W, Sn+Mn, Mn+Ge or combinations thereof, (2) Cr, Sb, Ce, Pn, Ge, B, Sn, Cu or combinations thereof, or (3) Mg+P, Mg+Cu, Mg+Cr, Mg+Cr+W, Mg+W, Mg+Sn or combinations thereof, a is 0 to 5, b is 0 to 20, c is 0 to 20, d is 0 to 20, e is 0.01 to 12 and x satisfies the valence requirements. The method of preparation disclosed was that solution A of ammonium molybdate, phosphoric acid, water and silica sol and solution B of ferric nitrate, bismuth nitrate, nickel nitrate, cobalt nitrate, cobalt nitrate and potassium nitrate were prepared and then solution B was added to solution A.
U.S. Pat. No. 5,245,083 discloses a catalyst for preparing methacrolein of a mixture of composition (1) of the formula:MoaBibFecXdZfOgwhere X is Ni and/or Co, Z is at least one of W, Be, Mg, S, Ca, Sr, Ba, Te, Se, Ce, Ge, Mn, Zn, Cr, Ag, Sb, Pb, As, B, P, Nb, Cu, Cd, Sn, Al, Zr and Ti, a is 12 b is 0.1 to 10, c is 0 to 20, d is 0 to 20, f is 0 to 4 and g satisfies the valence requirement and composition (2) of the formula:AmMonOpwhere A is at least one of K, Rb and Cs, m is 2, n is 1 to 9 and p is 3n+1. The method of preparation was that solution A of ammonium paramolybdate in water, solution B of cobalt nitrate and ferric nitrate in water, solution C of bismuth nitrate in aqueous nitric acid were prepared and solution B and solution C were added to solution A. Separately, ammonium molybdate was dissolved in water to form a solution to which cesium nitrate and nitric acid were added. The two resulting compositions were mixed to form a catalyst. In a comparative example, the cesium nitrate was dissolved in solution A such that only one composition was formed into a catalyst.
U.S. Pat. No. 4,537,874 discloses a catalyst for production of unsaturated aldehydes of the formula:BiaWbFecModAeBfCgDhOxwhere A is nickel and/or cobalt, B is at least one of alkali metal, alkaline earth metals and thallium, C is at least one of phosphorus, arsenic, boron, antimony, tin, cerium, lead and niobium, D is at least one of silicon, aluminum, zirconium and titanium, a is 0.1 to 10.0, b is 0.5 to 10.0, c is 0.1 to 10.0, d is 12, e is 2.0 to 20.0, f is 0.001 to 10.0, g is 0 to 10.0 and h is 0 to 30 and x satisfies the valence requirement. The ratio of a/b is 0.01 to 6.0 so that bismuth is combined very stably with tungsten and compounds such as bismuth trioxide and bismuth molybdate are not formed. The method of preparation disclosed was that bismuth nitrate was dissolved in water and nitric acid to form a solution to which aqueous ammonia was added to obtain a white precipitate which was collected as a yellow powder. Separately, aqueous solutions of cobalt nitrate, ferric nitrate, silica sol and potassium nitrate were added to an aqueous solution of ammonium molybdate to form a suspension to which the yellow powder was added. In one example, an aqueous solution of sodium tungstate was added to the bismuth nitrate solution.
U.S. Pat. No. 5,728,894 discloses a catalyst for producing methacrolein of the formula:Mo12BiaCebKcFedAeBfOxwhere A is Co or a mixture of Co and Mg having an atomic ratio of not more than 0.7, B is Rb, Cs or a mixture thereof, a is 0 to 8, b is 0 to 8, c is 0 to 1.2, d is 0 to 2.5, e is 1.0 to 12, f is 0 to 2.0 and x satisfies the valence requirement. The relative atomic ratio of iron to bismuth and cerium should be 0<d/(a+b+d)≦0.9. The relative atomic ratio of bismuth, cerium and potassium should be 0.05≦b/(a+b+c)≦0.7. The relative atomic ratio of potassium to bismuth and cerium should be 0<c/(a+b+c)≦0.4. Bismuth, cerium, potassium, iron and cobalt are indispensable elements for the disclosed invention. The method of preparation disclosed is that solution A of ammonium heptamolybdate and water and solution B of bismuth nitrate, cerium nitrate, iron nitrate, cesium nitrate, potassium nitrate and cobalt nitrate were prepared and solution A and solution B were mixed.
U.S. Pat. No. 4,916,103 discloses a catalyst for oxidation of propylene to acrolein and acrylic acid containing molybdenum, bismuth, iron, cobalt or nickel, phosphorus; at least one of arsenic, antimony, tin, thallium, tungsten, an alkaline earth metal, zinc and/or chromium; and at least one of sodium, potassium, rubidium, cesium and/or indium. The method of preparation disclosed was that ammonium heptamolybdate was dissolved in water and potassium hydroxide to form a solution to which iron molybdate, cobalt nitrate, bismuth tungstenate and silica sol solution were added.
U.S. Pat. No. 5,166,119 discloses a catalyst for producing methacrolein and methacrylic acid containing molybdenum, tungsten, bismuth, iron, antimony; at least one of nickel and/or cobalt; at least one of cesium and/or thallium; at least one of magnesium, manganese, zinc, barium and/or chromium; and at least one of phosphorus, boron, sulfur, silicon, cerium, potassium and/or rubidium. The method of preparation disclosed was that solution A of ammonium molybdate and cesium nitrate in water and solution B of bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and magnesium nitrate in nitric acid and water were prepared and solution B was added to solution A. In one example solution B was of bismuth nitrate and cobalt nitrate and there was an additional solution C of ferric nitrate and zinc nitrate which was added after solution B.
U.S. Pat. No. 5,276,178 discloses a catalyst for producing methacrolein and methacrylic acid containing molybdenum, tungsten, bismuth, iron; at least one of nickel and/or cobalt; at least one of alkali metal and/or thallium; at least one of alkaline earth metals; at least one of phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic and/or zinc; and at least one of silicon, aluminum, titanium and/or zirconium. The method of preparation disclosed is that cobalt nitrate and ferric nitrate were dissolved in water, bismuth nitrate was dissolved in aqueous nitric acid, cesium nitrate was dissolved in water and ammonium paramolybdate and ammonium paratungstate were dissolved in water. The first three solutions and silica sol were added to the last solution. A second catalyst with a less amount of cesium was prepared and used with the first catalyst in the isobutylene oxidation. In another example, no ammonium paratungstate was used, thallous nitrate and strontium nitrate were used in place of cesium nitrate, tellurium oxide, lead nitrate and zinc nitrate were added and titanium dioxide was used in place of silica sol. In another example, potassium nitrate, barium nitrate and beryllium nitrate were used in place of cesium nitrate, antimony trioxide and manganese nitrate were added and zirconium nitrate was used in place of silica sol.
U.S. Pat. No. 5,532,199 discloses a catalyst for producing acrolein and acrylic acid or methacrolein and methacrylic acid containing molybdenum, bismuth, iron; at least one of nickel and/or cobalt; at least one of magnesium, zinc, manganese, tin and/or lead; at least one of phosphorus, boron, sulfur, tellurium, silicon, selenium, germanium, cerium, niobium, aluminum, titanium, zirconium, tungsten and/or antimony; and at least one of potassium, sodium, rubidium, cesium and/or thallium. The method of preparation disclosed was that ammonium paramolybdate, ammonium paratungstate, cesium nitrate and antimony trioxide were added to water to form a first solution and bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, magnesium nitrate, zinc nitrate and boric acid were added to nitric acid and water to form a second solution which was added to the first solution.
U.S. Pat. No. 5,602,280 discloses a catalyst for producing acrolein and acrylic acid or methacrolein and methacrylic acid containing molybdenum, bismuth, iron; at least one of nickel and/or cobalt; at least one of manganese, zinc calcium, magnesium, tin and/or lead; at least one of phosphorus, boron, arsenic, tellurium, tungsten, antimony and/or silicon; and at least one of potassium, rubidium, cesium and/or thallium. The method of preparation is that solution A of ammonium molybdate and silica sol in water, solution B of nickel nitrate (or cesium nitrate), cobalt nitrate, ferric nitrate and thallium nitrate in water and solution C of bismuth nitrate in nitric acid and water were prepared and a mixture of solution B and solution C was added to solution A.
U.S. Pat. No. 5,856,259 discloses a catalyst for producing methacrolein and methacrylic acid containing molybdenum, bismuth, iron; at least one of nickel and/or cobalt; at least one of magnesium, zinc, manganese, tin and/or lead; at least one of phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium niobium, titanium, zirconium, tungsten and antimony; and at least one of potassium, sodium, rubidium, cesium and/or thallium. The method of preparation was that a first solution of ammonium paramolybdate, antimony trioxide, titanium dioxide and tellurium dioxide in water, a second solution of bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, magnesium nitrate and cesium nitrate in aqueous nitric acid were prepared and the second solution was added to the first solution. In another example, a first solution of ammonium paramolybdate, silicon dioxide and ammonium paratungstate in water and a second solution of bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, zinc nitrate, cerium nitrate, rubidium nitrate and potassium nitrate in aqueous nitric acid were prepared and the second solution was added to the first solution. In another example, a first solution of ammonium paramolybdate and zirconium dioxide and a second solution of phosphoric acid, bismuth nitrate, ferric nitrate, cobalt nitrate, manganese nitrate, lead nitrate, cesium nitrate, sodium nitrate in aqueous nitric acid were prepared and the second solution was added to the first solution. In another example, a first solution of ammonium paramolybdate, tin oxide and germanium dioxide in water and a second solution of boric acid, sulfuric acid, bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, zinc nitrate, thallium nitrate and cesium nitrate in aqueous nitric acid were prepared and the second solution was added to the first solution.
U.S. Pat. No. 6,028,220 discloses a catalyst for producing acrolein and acrylic acid containing molybdenum, bismuth, nickel, cobalt, iron; at least one of tin, zinc, tungsten, chromium, manganese, magnesium, antimony and/or titanium; and at least one of potassium, rubidium, thallium and/or cesium. The method of preparation disclosed was that solution A of ammonium molybdate and potassium nitrate in water and solution B of cobalt nitrate, nickel nitrate and ferric nitrate in water and solution C of bismuth nitrate in water and nitric acid were prepared and a mixture of solution B and solution C was added to solution A.
Prior art discloses different methods of making mixed metal oxide catalysts which contain molybdenum, bismuth, iron, cesium and other metals for the production of methacrolein. The advantages of a particular method of making or order of addition wherein the water soluble compounds and the water insoluble compounds are prepared separately and then mixed to form the catalyst has not been disclosed.